Modulation of circularly polarized luminescence through excited-state symmetry breaking and interbranched exciton coupling in helical push–pull organic systems

Abstract

π-Helical push–pull dyes were prepared and their (chir)optical properties were investigated both experimentally and computationally. Specific fluorescent behaviour of bis-substituted system was observed with unprecedented solvent effect on the intensity of circularly polarized luminescence (CPL, dissymmetry factor decreasing from 10⁻² to 10⁻³ with an increase in solvent polarity) that was linked to a change in symmetry of chiral excited state and suppression of interbranched exciton coupling. The results highlight the potential of CPL spectroscopy to study and provide a deeper understanding of electronic photophysical processes in chiral π-conjugated molecules.